He and teammate Bencic are the defending champions at Hopman. The Swiss pair served great in the opening set, breaking Tiafoe in the fifth game after a return victor from Bencic and taking the opener after a hold at love from Roger a few minutes later.
Federer and Williams, of course, won't be the only players on the court in a mixed doubles match.
In the biggest mixed doubles drawcard in the 31-year history of the tournament, in what is expected to be its final edition, Federer teamed with Belinda Bencic to win the match in straight sets under the Fast4 format and win the Group B tie for Switzerland. The US lost to Greece on Monday, though Williams won her singles match.
Williams enjoyed a strong opening service game in the mixed doubles, with two of her serves proving too hard to handle for Federer.
However in the doubles match the Greek team of Tsitsipas and Sakkari emerged victorious 2-1 (4-1 1-4 4-2) over Williams and Tiafoe to win the tie by the same score.
"I'm happy in all aspects of my game that things were working - foot work, offensive play, serve, return - it was all there".
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And the 20-time grand slam victor, who will attempt to win a third straight Australian Open title later this month, was satisfied with where his form and fitness is at.
"I was so excited and literally it was the match of my career", she said.
"I have been looking forward to it", she told The New York Times.
Federer's sublime touch at the net proved decisive as he moved closer to a record third Hopman Cup title.
The pair battled it out for over two hours in their first round match before Venus broke through in the sixth game of the decider to set up victory.
Williams led 4-1 in the first set before Bencic fought back to win the next five games.
Federer's response? "It's the age of social media", he said, laughing at the prospect of Williams' plan.
'People talk about her serve so much and I see why it's such a wonderful serve - you just can't read it'. "I knew I could play better, so that was always something that was in my mind".